Chemicals for water repellence



cnrmoaps roe warm REPELLENCE Edgar Wolf, Krefeld, Germany,

assignor to Heberlein Patent Corporation, New York, N. Y., a corporation of New York No Drawing.

Application March 12, 1938, Serial No. 195,600. In Germany March 15, 1937 11 Claims.

This invention relates to water-repellent textiles, chemicals for producing water-repellence, and processes for manufacturing such textiles and chemicals.

This invention may also be said to relate to alternative or improved water-repellents and the processes for making same, useful in a manner generally similar to the water-repellent compounds and treatments disclosed in my copending application Ser. No. 177,054, filed November 29, 1937, reference to which is hereby made.

I have found that in general the compounds mentioned, one may produce water-soluble quaternary compounds. Such compounds comprise highly desirable products for the treatment of textile materials for water-repellence upon properly combining such materials with such products under reaction conditions.

The objects of the invention accordingly include the provision of improved water-repellent textiles treated with compounds of the above indicated character, and the production'of the novel chemical compounds, and provision of improved processes for .making such chemicals adapted for use in producing such water-repellent textile materials, among other possible uses. Further and more specific objects, features and advantages of the invention will more fully appear from the following specification.

The invention consists in the novel products as well as the novel processes and steps of procconversion products obtained in this manner may then be converted as by the use of pyridine, 2- methyl-pyridine, triethyl-amine, or equivalent tertiary bases, into quaternary ammonium compounds. Such compounds are remarkably eifeotive in imparting water-repelling properties to textile material when 'properly applied thereto,

in a manner generally similar to the application of the water-repellent chemicals to the textiles as disclosed by said copending application. That is, the water-repelling effect is'fast to washing or laundering with soap solutions and to dry cleaning with benzine for example. Furthermore, the fastness to washing of the substantive dyestuffs of the treated textile material is substantially improved. And in connection with rayon fabrics produced from cellulose, it is pos sible by means of the process to effectively increase the fastness of suchdyestu'fis both against deterioration by moisture and under dry conditions. Such compounds are also suitable for addition to baths serving for imparting creaseor wrinkle-resistant properties to textiles. I

In cases where the acyl halides, for example, are converted by the use of substituted ammoniaformaldehyde condensation products, a compound of the general formula R'.X.NH2 is first converted with formaldehyde or trioxymethylene. The converted product is treated with the acyl chloride. In the formula R'.X.NH,- as herein used, R represents an alkyl radical (such for "example as C17H35), a cycloalkyl radical for esses according to which such chemical and I textile products are manufactured, specific emby way of various examples according to which I now prefer to practice the invention.

In accordance with the present invention the acyl halides above mentioned may have the general formula-R. Co halide, in which R is an aliphatic or aliphatic-aromatic radical in which the aliphatic portion has at least ten carbon atoms. The conversion of such acyl halides with hexan ethylenetetramine [(CI-Iz) N4] is preferably effected with a molar'ratio of four parts of acid halide to one part of hexamethylenetetramine. The quantity vof he'xamethylenetetramine used, however, may also be increased for example to a ratio in the neighborhood of three moles of the acid halide to one mole of the hexamethylenetetramine. The r e-s u 1 tin g example cyclohexylamine C6H11.NH2, or an aralkyl radical (CwHaaphenyl for example), and X indicates methylen or the C=0 or S02 group. In place of the fatty acid chlorides, one may also use the corresponding chlorocarbonic acid (ROCOCI) or carbamic acid ester chlorides (carbamido chlorides), such as CmHsvNHCOCl, for example. As the tertiary bases to be used in such cases, one may for example use the volatile tertiary bases such as pyridine and its homologs, or trimethylamine, triethylam'ine etc. The resulting products may be used for the same purposes with substantially the same results above specified cording to the invention, carried out in various ways now preferred. It is to be understood that the invention is not limited to any of these particular examples or others as hereinafter given,

except as indicated in the appended claims.

Examples 1. '140 parts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; 1208, parts formed. Thereupon-1500 grams of stearyl chloride are added, the whole is well stirred and 400 Y of stearic acid chloride (CnHasCOCl) are added and the whole is heated for one hourin a reflux condenser. The chloroform is thereupon drawn of! by suction in vacuum and the conversion product is stirred with 320 parts of pyridine. 6'

point after recrystallization from petroleum lether is about 115 C. (with splitting of! of form-.

aldehyde).

2. 1208 parts of stearic chloride are diluted with about the same quantity .of benzol or carbon tetrachloride and 140 parts'of finely pulverized l of p-stearyl-oxy-benzoic-acid chloride hexamethylenetetramine are added. After heating for two hours on a boiling water -bath, the

solvent is drawn off by suction in vacuum and the conversion product is stirred with 320 parts of pyridine. water soluble. Its melting point is about 115 C.

. 3. 140 parts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; thereupon, 1768 parts of montanicchloride C2vHs5.COCl are i added, and the whole is heated for one hour in a like mass obtained is now soluble ii -hot water.

the reflux condenser. The benzol is thereupon drawn off by suction in vacuum and 320 parts of pyridine are, stirred with the reaction product. The water-soluble waxlike compound obtained has a melting point. of about 110 C. I I

4. 140 parts of finely pulverized hexamethylenetetramine are stirred with 1208 parts of stearic chloride and heated, while stirring constantly, for one hour, at about 110 C. Thereupon; 320 parts of pyridine are added, while stirring. The

wax-like water-soluble product has a melting point of about 115C. 7

5. 1350 grams of the conve ion product ob-' tained in accordance with Example 1 from stearic chloride and hexamethylenetetramine are mixed while stirring, with 37-2- grams of 2-methyl-pyridine. The quaternary ammonium compound of 2-methyl-pyridine is produced with development of heat. The product is water-soluble.

6. 1350 grams of the conversion product obtained in accordance with Example 1, from stearic chloride and hexamethylenetetramine are stirred with 404 grams of triethylamine. The quaternary ammonium compound of triethylamine is produced withsimultaneous development of heat. The product is water-soluble.

'7. 140 parts of finely pulverized (powdered) hexamethylenetetramine are dissolved in, 1400 'partsof chloroform and 1340 parts of chlorocarbonic-acid-octadecyleester CmHsLOCOCl are added; the whole is heated for one hour inthe reflux condenser, the solvent is drawn on by suction in vacuum and to the residue, 320 parts of pyridine are added, while stirring. The prod: not is water-soluble. I

8. 850 grams of para toluol sulfonamide,

CH3.CaH4.SO2NH2 are melted with 300 grams of trioxymethylene (C1120): at a temperature of 110-l20 C. until the coni'lensittion productis grams of pyridine are added. The product is 7 water-soluble.

9. 400 grams of stearic-acid-amide ,cnmecomn are melted with 85 grams of trioxymethylene (C1120): at a temperature of 110-120 C. until the condensation product is formed. Thereupon The wax-like resulting product is 20 2 mangoes dissolved in 1400 parts of chloroform; 906 parts of stearic acid. chloride (CmHasCOCl) are added and the whole is heated for one hour in a refluxv condenser; The chloroform is thereupon drawn off by suction in vacuum and the conversion prod- -not is stirred with 240 parts of pyridine, There occurs the formation of the quaternary pyridin- .ium compound with the simultaneous development of heat. The white wax-likemass obtained is now soluble in hot water.

11. 140 parts of hexamethylenetetramine are dissolved in 1400 parts of chloroform; 1692 grams (C11H35.CO.O.pheny1.COCl) Although I have described the chemical compounds above as quaternary ammonium salts made with a tertiary amine, it will be understood 0 that I may employ the compounds without such addition of tertiary amine, or other water-solubilizing agent. If such material is omitted from 'the various compounds above, theyare nevertheless useful for treatment of textiles in a. sim- 3 iiar' manner to that herein described, but the treatment is preferably carried out by dissolving the materials in benzine or similar solvent: An

example of such treatment is given below.

The following comprise specific examples of 0 methods now preferred fortreating various textile materials according to the invention.

12-. A cloak fabric which consistsof spun rayon in warp and weft is impregnated in an aqueous 1 solution which contains, per liter, 15 grams ofthe quaternary pyridine compound prepared according to Example 1, from hexamethylenetetramine,

stearic acid chloride and pyridine. The bath also contains 5 grams per liter of sodium acetate. The temperature of the bath is about 40 C. After the w impregnation the material is dried and is then subjected for approximately one hour to a heat treatment in a drying chamber at about 120 C.

313. Cotton calico is passed through an aqueous solution which contains 15 grams per liter of a quaternary pyridinium compound prepared according to Example 3 from hexamethylenetetramine, montanic acid chloride and pyridine. The

bath also contains 5 grams per liter of sodium acetate. Thesaid fabric is passed through the said aqueous solution while the latter is at about 40 C. Thereafter the impregnated material is dried. and thereupon subjected to heat treatment a in a drying chamber at about 120 C. for 2 hours.

14.. Bleached wool gabardine is passedthrough aliaqueous solution which contains 20 grams per liter of a quaternary. pyridinium compoundas' described in Example 12. The impregnated material is dried and thereupon subjected to heat treatment in a drying chamber at about C.-

for 4 hours.

' '15. A crepe de chine fabric which consists of real silk in warp and weft is impregnated in an aqueous solution which contains per liter 15 grams of the quaternary pyridine compound pre- 350 grams of stearyl chloride are added and pared accordingto Example 1, from hcxaniethylenetetramine, stearic acid chloride and pyridine. The bath also contains grams per liter of sodium acetate. The temperature of the bath is about 40 C. After the impregnation the material is dried and is then subjected for approximately two hours to a heat treatment in a drying chamber at about 110 C. u

16. A clothing material of spun viscose rayon is impregnated in an aqueous solution of 5 grams per liter of sodium acetate,following the impregnation it is wrung out, dried, and passed through a 1% solution of the conversion product of hexamethylenetetramine and stearic acid chloride in carbon tetrachloride The solvent is evaporated and the material is subjected for five minutes to a temperature of 110 C;

In consequence of the water-solubility of the quaternary ammonium compounds of my invention, the treatment of the textile material for thepurpose of increasing the resistance to wetting and diminution of swelling capacity can advantageously be combined with a treatment for increasing the resistance to wrinkling, which is ordinarily carried out also in an aqueous bath; thus for the purpose of imparting water-repelling properties and wrinkle-resistance, a single aqueous bath may be employed containing not only the said quaternary ammonium compounds of my invention butalso artificial resin or artificial resin initial condensation product or the formative components for the preparation of an artificial resin. Formaldehyde with ammonium chloride or other non-alkaline catalyst may be employed in placeof the resin or resin components for producing wrinkle-resistance, and with this may be employed the quaternary ammonium compounds of my invention for producing water-repellence. The processesthus employed in combination will produce a textile material having both water-repellence' and wrinkle-resistance.

17. A plush fabric, consisting of cotton in warp and weft and artificial silk spun fiber in the pile,

ispassed through an aqueous bath which contains, per liter, 250 grams of aformaldehyde-urea condensation product which is on the market I under the name Kaurit, 6 grams of primary sodium phosphate, 6 grams of secondary sodium phosphate, 2 gramsof tartaric acid, and 15 grams of the quaternary pyridine salt prepared accord ing to Example 3 from hexamethylenetetramine,

montanic acid chloride and pyridine. .After the impregnation thematerial is squeezed out, brushed, dried and treated for about 60 minutes at about 110 C. In this manner the fabric re-, ceives a water-repelling and wrinkle-resistant finish, inwhichconnection the water-repelling efiectis' proof even to dry-cleaning and washing with soap.

'18., A sample of "transparent velvet comprising,

a silk backing and viscose rayon pile'is passed through an aqueous bath at 40-C.

for 2 seconds which contains per liter:

Formaldehyde 40% solution i. cc 40o Ammonium chloride grams 1 5- The quaternary pyridine salts do 15 such as employed in Example 17.

After; impregnation the material is squeezed .out, rolled up and remains untreated for 20 minutes. The velvet is then stretched upon a stenter frame and dried at a temperature of about 100 C. During the drying process the velvet pile is brushed. After drying the velvet is further greeted 60 minutes at a temperature oi about The newcompoundsdscribed above can also be added to the spinning solutions of viscose and cupranunonium cellulose to produce a filament having water-repellentproperties.

19. 20 parts of the quaternary ammonium compound obtained in accordance with Example 6 from stearic acid chloride, hexamethylenetetramine and trimethylamine are stirred to a paste with 40 parts of hot water;. and are added to 1000 parts of a viscose solution having 5% of cellulose; the whole is homogenously mixed and is spun in' well-known fashion. The precipitating bath which I prefer to employ contains sulphuric acid (8-l0%)with the addition of ammonium sulphate or and other salts and glucose at a temperature of 40 C. The temperature and rate of spinning are substantially the sameas those practised commercially. The spun filament is dried and then heated to 90 C. for 60 minutes. The completed thread manifests water-repellent properties and is of extraordinary softness.

The expression ammonia-formaldehyde compound as used in the appended claims, is intended to cover compounds of formaldehyde and ammonia and substituted ammonia such as herein described.

While the invention has been describedin detall with respectto various preferred products and preferred methods of making the sai'ne, it

will be obvious to those skilled in the art after understanding the invention, .that further changes and modifications may be made there-H in without departing from the spirit or scope of the invention, and it is intended in the appended claims to cover all such changes and modifications.

What is claimed as new and desired to be secured by Letters Patent is:

1. A process for the productionof quaternarythe amount of hexamethylenetetramine by molar ratio, and treating the resulting conversion product with a tertiary base to -convert such product to a quaternary ammonium compound.

2. A process for the production of quaternary ammonium compounds,which comprises reacting hexamethylenetetramine, in the presence of heat and an inert solvent with an acyl chloride having an aliphatic radical of at least ten carbon atoms, and treating the resulting-conversion product with apyridine to convert, such product to a quaternary ammonium compound.

3. A process for the production of quaternary ammonium compounds,, which comprises reacting hexamethylenetetramine in the presence of heat and an inert solvent with a chlorocarbonic ,acid ester halide havingqan aliphatic radical of at leastten carbon atoms, and treating the re-" suiting conversion product with a pyridine to convert such product to a. quaternary ammonium compound.

'4. A process for the production of quaternary ammonium compounds, whicncomprises reactinghexamethylenetetramine' in the presence of heat and an inert solvent with a carbamic acid halide having an aliphatic radical of at least ten car-' bon atoms, and treating the resulting conversion product with a pyridine to convert such product a quaternary ammonium compound.

- therein the t 5. A'process of the character described, which comprises: reacting hexamethylenetetramin'e in the presence of heat and an inert solvent with a compound having the linkage-C:O. halide selected from the group consisting of fatty acid halides, carbonic ester halides and carbamic acid halides.

ing at least ten carbon atoms. and with a tertiary amine.

6. A process for the production of quaternary 8. A condensation product prepared by reactin'g hexamethylenetetramine, under conditions such that decomposition of the latter does not take place, with a carbonic ester halide contain- Patent No '22h2, 565i 9. A condensation product prepared by reacting hexamethylenetetramine, under conditions such that decomposition of the latter does not take place, with a carbamicacid halide containing at least ten carbon atoms, and with a tertiary amine.

- 10; A condensation product prepared by reacting hexamethylenetetramine, under conditions such that decomposition of the latter does not take place, with a compound containing at least ten carbon atoms and selected from the groupi consisting of fatty acid halides, carbonic ester halides and carbamic acid halides.

11. A condensation product prepared by reacting hexamethylenetetramine, under. conditions such that decomposition of the latter does not take' place, with a compound containing at least ten carbon atoms and selected from the group consisting oi Iatty. acid halides, carbonic esterhalides'and carbamic acid halides, combined with a tertiary amine.

WCERTIFICATE v0F CORRECTION.

May 20, 19ml.

EDGAR WOLF-- A,

. I I 1) I 11: is hereby certified that error appearsin the printed specification or the above numbered patent requiring correction as follows: Page 1, first col mn, line" 1 9, fer "12.00" to, strike out the word "est er" Office read -R.'co--;-

. and insert the 57 and that the said' Letters Patent should be the same may conform to the record same page, second column,- line same after "acid" in line read with this correction oi the case in .thelPatent signed and sealed them a of y, 191411 i seai) Van Arsdale, acting Conhiissioner of Patents.

EDGAR wow.

1.CERTIFICATE OF CORRECTION. Patent No. '2,-2L;2,565: V May 20, 19m.

EDGAR WOLF.

v v It is hereby. certified that error appears .in the printed specification Of the above numbered patent requiring correction as follows; Page 1, first column, 1ineh.9, for "12.00" read -R.CO-; same page, second column, line 4.0, etrike out the word "ester" and insert the same after "acid" in line 57 and that the said- Letters Patent should be read with this correction therein tl'nt the same may conform to the record of the case in the Patent Office. Signed and sealed this vn+1 a of July, A. D. 1 9L;l.

- Henr van Arsdele, a Acting Comnis sioner of Patents. 

